The present invention relates to the use of subatmospheric pressure to expedite refining of molten glass or the like. More particularly, the invention relates to enhancement of the foaming in such a refining technique to yield improved refining.
In the melting of glass, substantial quantities of gas are produced as a result of decomposition of batch materials. Other gases are physically entrained by the batch materials or are introduced into the melting glass from combustion heat sources. Most of the gas escapes during the initial phase of melting, but some becomes entrapped in the melt. Some of the trapped gas dissolves in the glass, but other portions form discrete gaseous inclusions known as bubbles or "seeds" which would be objectionable if permitted to remain in unduly high concentrations in the product glass. The gas inclusions will rise to the surface and escape from the melt if given sufficient time in the stage of a melting operation known as "refining" or "fining." High temperatures are conventionally provided in the refining zone to expedite the rise and escape of the gaseous inclusions by reducing the viscosity of the melt and by enlarging the bubble diameters. The energy required for the high temperatures employed in the refining stage and the large melting vessel required to provide sufficient residence time for the gaseous inclusions to escape from the melt are major expenses of a glassmaking operation. Accordingly, it would be desirable to assist the refining process to reduce these costs.
It has been known that reduced pressure could assist the refining process by reducing the partial pressure of the included gaseous species and by increasing the volume of bubbles within the melt so as to speed their rise to the surface. The impracticality of providing a gas-tight vessel on the scale of a conventional refining chamber so as to draw a vacuum therein has limited the use of vacuum refining to relatively small scale batch operations such as disclosed in U.S. Pat. Nos. 1,564,235; 2,781,411; 2,877,280; 3,338,694; and 3,442,622.
Continuous vacuum refining processes have been proposed but have not found acceptance for large scale, continuous manufacture of glass due to various drawbacks. In the continuous vacuum refining arrangements shown in U.S. Pat. Nos. 805,139; 1,598,308; and 3,519,412 a disadvantage is the requirement for relatively narrow vertical passageways leading into and out of the vacuum zone necessitated by the pressure difference. Also, the molten glass is not fully exposed to the vacuum since the incoming glass enters from below a pool of glass.
A different arrangement is shown in U.S. Pat. No. 3,429,684, wherein batch materials are fed through a vacuum lock and melted at the top of a vertically elongated vacuum chamber. Melting raw materials within the vacuum chamber is a disadvantage of that arrangement for three reasons. First, large volumes of foam would be created by carrying out the initial decomposition of the raw materials under vacuum, which would require a vessel large enough to contain the foam. Second, there is a danger that raw materials may follow a short circulation path to the output stream, thus avoiding adequate melting and refining. Third, carrying out the initial stages of melting and heating the melt to a refining temperature within the vacuum vessel require large amounts of heat to be supplied to the melt within the vessel. Such a major heat input to the vessel inherently induces convection currents within the melt that increase erosion of the walls, which leads to contamination of the refined product stream.
U.S. Pat. No. 4,195,982 discloses initially melting glass under elevated pressure and then refining the glass in a separate chamber at a lower pressure. Both chambers are heated.
A preferred technique for vacuum refining glass is disclosed in U.S. Pat. No. 4,738,938 (Kunkle et al.) wherein the creation of foam is deliberately enhanced by introducing the molten glass into the vacuum chamber above the level of the molten glass held therein. Excessive foam was indicated in that patent as being a problem to be avoided. A large space above the liquid container must be provided to accommodate the foam if a large throughput is desired. Since this headspace must also be maintained gas-tight, its construction can be a significant economic drawback, particularly on a large scale process. As a result, the volume of foam acts as a limiting factor to the throughput rate and/or the degree of vacuum that can be utilized.
One measure for maintaining reasonable foam volume that is disclosed in U.S. Pat. No. 4,738,938 is to minimize and, preferably, to eliminate the presence of sulfur, generally present in the form of SO.sub.3, in the molten glass entering the vacuum chamber. The use of sulfur compounds is common in the glassmaking art as melting and refining aids. But in the vacuum refining technique of the aforesaid patent, the inclusion of sulfur compounds was disclosed to be unnecessary and to be a major source of unwanted foam. Excessive foam generation can result if the molten glass contains sulfur refining aids on the order typically provided in conventional melting and refining operations. Following the teachings of addition of refining aids such as sulfur compounds has been eliminated, and refining has generally been adequate. However, on some occasions, for reasons that were previously not understood, periods of inadequate removal of gaseous seeds from the glass occurred, even though the glass entering the vacuum refiner was very low in gas content and low pressures were used.
U.S. Pat. No. 2,331,052 (Shadduck) discloses bubbling steam through molten glass to refine the glass by sweeping out other gases.
U.S. Pat. No. 3,617,231 (Fenstermacher) discloses increasing the water content of the product glass in order to alter its softening point. Water concentrations of the product glass as high as 0.066 percent by weight are disclosed.
U.S. Pat. No. 3,606,825 (Johnson) uses submerged combustion of methane with oxygen to melt glass. Although the chief product of combustion would be water, the patent expresses no interest in increasing the water content of the glass, only avoiding the introduction of nitrogen bubbles. A similar use of oxygen fired submerged combustion is disclosed in U.S. Pat. Nos. 4,545,800 (Won et al.) and 4,539,034 (Hanneken).